JPH09208556A - Production of aminoester compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aminoester compound in high yield without carrying out a complicated procedure, by reacting an amino-alcohol compound or its N-acetylated substance with sulfuric acid or fuming sulfuric acid in a specific solvent and distilling away water, etc. prepared as by-products together with the solvent. SOLUTION: An amino-alcohol compound of formula I (W1 is a 2 6C alkylene; R1 is H, a 1-4C alkyl, phenyl or W1 -SO2 CH2 CH2 OH) (shown as a free form) or its N-acetylated substance is reacted with sulfuric acid or fuming sulfuric acid in an organic solvent to be separated from water under normal pressure or reduced pressure and water or water and acetic acid are distilled away together with the organic solvent to give an aminoester compound of formula II [W2 is a 2-6C alkylene; R2 is H, an alkyl, phenyl or W2 -SO2 CH2 CH2 OY' (Y' is H or SO3 H); Y is shown as Y']. The aminoester compound is useful as an intermediate for a water-repellent and oil-repellent processing agent, a setting agent for silver halide photography, a surfactant, a dye, a medicine, an agrochemical, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an amino ester compound.

[0002]

2. Description of the Related Art Various industrial products, especially water and oil repellent finishing agents,
As a method for producing an amino ester compound useful as an intermediate for silver halide photographic hardeners, surfactants, dyes, pharmaceuticals, agricultural chemicals, etc., conventionally, when an aliphatic amino alcohol compound is esterified with sulfuric acid, an amino alcohol compound is used. In a large excess of concentrated sulfuric acid, an N-acetylated amino alcohol compound is hydrolyzed in hydrochloric acid or diluted sulfuric acid, and then esterified in a large excess of concentrated sulfuric acid, amino alcohol compound and chlorosulfone. Acid N
-It was carried out by a method such as reacting in methylpyrrolidone at 10 to 80 ° C.

[0003]

However, in the above method, there is a problem that the operation is complicated because it is necessary to dry the aliphatic aminoalcohol compound as the raw material. In addition to the need to dry the N-acetylated product of the amino alcohol compound, the yield of taking out the target compound, an amino ester compound, was low, and neither was industrially advantageous. Further, in the above method, excess chlorosulfonic acid in the reaction solution is first decomposed with ice water, the solution obtained by the decomposition is neutralized, and then the amino ester compound is treated with N-methylpyrrolidone from the neutralized solution. It is not only necessary to extract with a suitable solvent other than N.
-Methylpyrrolidone also had to be recovered, which was not industrially advantageous.

[0004]

Means for Solving the Problems As a result of intensive studies on an industrially advantageous improved method for producing an aminoester compound, the present inventors have found that an aminoalcohol compound or its N-acetylated product and sulfuric acid or fuming sulfuric acid are used. , In an organic solvent which separates from water, under normal pressure or reduced pressure, by-product water or water and acetic acid, while reacting while distilling off with the organic solvent, the reaction without complicated operations And that the yield of the reaction product taken out is significantly improved,
The present invention has been completed.

That is, the present invention, when expressed in (i) free form,
The following general formula (II) H-N (R₁) -W₁-SO_TwoCH_TwoCH_TwoOH (II) [wherein W₁Is a halogen atom, hydroxy group, sulfa
Group, carboxy group, cyano group or sulfo group
Optionally substituted, -O- or -NR_Three-(Here
And R_ThreeIs a hydrogen atom or C₁~ C_FourRepresents an alkyl group
You. ) A straight-chain or branched C which may contain_Two~ C
₆R represents an alkylene group;₁Is a hydrogen atom, substituted
May be C₁~ C_FourAlkyl group, may be substituted
Phenyl group or -W₁-SO_TwoCH_TwoCH_TwoOH group
Represents ] The amino alcohol compound or
The N-acetylated product is separated from sulfuric acid or fuming sulfuric acid and water
Water or water and acetic acid under normal pressure or reduced pressure in an organic solvent
And react with the organic solvent while distilling off
In the free form, the following general formula (I) H-N (R_Two) -W_Two-SO_TwoCH_TwoCH_TwoOY (I) [wherein W_TwoIs a halogen atom, hydroxy group, sulfa
Group, carboxy group, cyano group or sulfo group
Optionally substituted, -O- or -NR_Three− (R_Three
Represents the same meaning as described above. ), Which may contain a straight chain
Shaped or branched C _Two~ C₆R represents an alkylene group;_Two
Is a hydrogen atom, optionally substituted C₁~ C_FourAlkyl
Group, optionally substituted phenyl group or -W_Two-SO
_TwoCH_TwoCH_TwoRepresents a group of OY ', Y and Y'are the same
Or differently, a hydrogen atom or -SO _ThreeRepresents H, but Y
And Y ′ are not hydrogen atoms at the same time, and R_Two
Is a hydrogen atom, optionally substituted C₁~ C_FourAlkyl
When it is a group or an optionally substituted phenyl group,
Y is not a hydrogen atom. ]
A method for producing an amino ester compound,

Further, (ii) the aminoalcohol compound represented by the above general formula (II) or its N-acetylated product in sulfuric acid or fuming sulfuric acid and an organic solvent which separates from water, under normal pressure or reduced pressure, Amino ester represented by the above general formula (I), which is characterized by reacting water or water and acetic acid together with the organic solvent by distillation, and then treating the obtained reaction product with water or ice. A method for producing a compound is provided. Hereinafter, the present invention will be described in detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The aminoalcohol compound represented by the general formula (II) or its N-acetylated product may be a free amine, or a mineral acid salt such as sulfate may be used. These free amine and mineral acid salt can be used in a water-containing state or a dry state. Further, the amino alcohol compound represented by the general formula (II) or its N-acetylated compound is NaC
It may contain an inorganic salt such as l or Na ₂ SO ₄ . In the present invention, N of the amino alcohol compound represented by the general formula (II) is
-When an acetylated product is used as a starting material, it is necessary to remove acetic acid by-produced by hydrolysis of the acetylamino group to the outside of the reaction system.

The concentration of sulfuric acid used in the reaction is not particularly limited, but is preferably 20 to 100%, more preferably 40 to 100%.
The concentration is adjusted to 98%. When fuming sulfuric acid is used, its concentration is preferably 30% or less. Further, sulfuric acid and fuming sulfuric acid may be used in combination. 100% use of sulfuric acid or fuming sulfuric acid
In terms of sulfuric acid, it is preferably 1 to 5 mol, and particularly preferably 1 to 3.5 mol per 1 mol of the aminoalcohol compound represented by the general formula (II) or its N-acetylated product. When the aminoalcohol compound represented by the general formula (II) or its N-acetylated product has two or more hydroxy groups, sulfuric acid or fuming sulfuric acid is converted into 100% sulfuric acid,
It suffices to use an amount capable of converting at least one β-hydroxyethylsulfonyl group into a β-sulfatoethylsulfonyl group, but use a 1-fold molar amount relative to the theoretical amount per hydroxy group. Is more preferable. The case where the aminoalcohol compound represented by the general formula (II) or its N-acetylated product has two or more hydroxy groups including hydroxy of the β-hydroxyethylsulfonyl group, and one β -When using an amount of sulfuric acid or fuming sulfuric acid capable of converting a hydroxyethylsulfonyl group into a sulfate ethylsulfonyl group, some of the hydroxy groups remained unconverted,
An aminoester compound represented by the general formula (I) is produced.

In the present invention, the order of charging the aminoalcohol compound represented by the general formula (II) or its N-acetylated product, and sulfuric acid or fuming sulfuric acid is not particularly limited. The reaction temperature is preferably in the range of 50 to 200 ° C,
More preferably, it is in the range of 70 to 150 ° C. Distillation of water or water and acetic acid out of the reaction system is usually carried out by stirring or mixing under normal pressure, but in some cases, in order to facilitate the distillation, nitrogen, air and carbonic acid are added to the reaction solution. A method of blowing an inert gas into a reaction such as gas may be adopted,
It may also be carried out by stirring or mixing under reduced pressure. At the time of distillation, an inert substance such as diatomaceous earth, activated carbon, silica gel or talc may be added to the reaction system to facilitate stirring or mixing, and the amino ester compound represented by the general formula (I) may be added to the reaction system. You may add a small amount to. The organic solvent that separates from water is a property that can be separated when mixed with water, is inert to sulfuric acid and fuming sulfuric acid, and can be distilled off together with water or water and acetic acid at the reaction temperature. An organic solvent having Preferred organic solvents include, for example, cyclohexane, aliphatic hydrocarbons such as heptane and octane, aromatic hydrocarbons such as benzene, toluene, xylene and solvent naphtha, dichloroethane, trichloroethane, dichloropropane, trichloroethylene, tetrachloroethane, and perfluoroethane. Examples thereof include halogenated hydrocarbons such as chloroethylene, chlorobenzene, and dichlorobenzene, nitrated hydrocarbons such as nitrobenzene, and ketones such as methyl isobutyl ketone. The amount of the organic solvent used is represented by the general formula (II)
Is preferably 0.1 to 10 times the weight of the amino alcohol compound or its N-acetylated compound,
Particularly preferably, the weight is 0.1 to 5 times. The method for producing the aminoester compound of the present invention can be carried out by using a batch type or continuous type reactor such as an ordinary can, a tank and a kettle, and a batch type or continuous type kneading in which kneading is performed with a strong force. This can be done by using a Japanese machine.

The aminoalcohol compound represented by the general formula (II) can be prepared by a known method, for example, by condensing the corresponding chloro or bromoalkylamine with mercaptoethanol, and then using the obtained thioether compound with hydrogen peroxide. It is manufactured by a method of oxidizing by oxidation. In the case of the N-acetylated compound of the aminoalcohol compound represented by the general formula (II), the thioether compound obtained by condensation is acetylated with acetic anhydride, and the acetylated product obtained is oxidized with hydrogen peroxide. It is manufactured by the method. General formula (II)
Examples of the aminoalcohol compound and the N-acetylated compound represented by the following include the following compounds in the form of a free amine.

H ₂ NC ₂ H ₄ SO ₂ C ₂ H ₄ OH H ₂ NC ₃ H ₆ SO ₂ C ₂ H ₄ OH H ₂ NC ₄ H ₈ SO ₂ C ₂ H ₄ OH H ₂ NC ₅ H ₁₀ SO ₂ C ₂ H ₄ OH H ₂ NC ₆ H ₁₂ SO ₂ C ₂ H ₄ OH H ₂ NC ₂ H ₄ OC ₂ H ₄ SO ₂ C ₂ H ₄ OH H ₂ NC ₂ H ₄ OC ₃ H ₆ SO ₂ C ₂ H ₄ OH HN (C ₂ H ₄ SO ₂ C ₂ H ₄ OH) ₂ H ₂ NC ₂ H ₄ NHC ₂ H ₄ SO ₂ C ₂ H ₄ OH _{CH 3 CONHC 2 H 4 SO 2} C 2 H 4 OH CH 3 CONHC 3 H 6 SO 2 C 2 H 4 OH CH 3 CONHC 4 H 8 SO 2 C 2 H 4 OH HN (C 6 H 5) -C 2 H ₄ SO ₂ C ₂ H ₄ OH

The amino ester compound represented by the general formula (I) is preferably taken out by treating the reaction product obtained after completion of the reaction with water or ice. Specifically, for example, in ice water or cold water, or for example, sodium bicarbonate, potassium hydrogen carbonate, soda ash, potassium carbonate,
The reaction product obtained after completion of the reaction can be added to ice water or cold water containing an alkali such as sodium hydroxide and potassium hydroxide, and taken out in a liquid state. Alternatively, ice water or cold water may be added all at once to the reaction product obtained after completion of the reaction. When the reaction product is added to ice water or cold water and taken out in a liquid state, or when ice water or cold water is added to the reaction product at once and taken out in a liquid state, the taken out liquid In addition, the alkali may be added. Further, the aminoester compound represented by the general formula (I) can be isolated from the liquid thus taken out by a known method such as liquid separation, washing, concentration, lyophilization and filtration. The aminoester compound represented by the general formula (I) may exist in a free form, and
It may be present in the form of a mineral acid salt such as sulfuric acid. Further, when the amino ester compound has an acidic water-soluble group such as a phenolic hydroxyl group, a sulfate group, a carboxy group and a sulfo group, these acidic groups are present in the form of an alkali metal or alkaline earth metal salt. May be.

[0013]

EXAMPLES Next, the method of the present invention will be described more specifically by way of examples. Parts and% in the examples mean parts by weight and% by weight, respectively.

Example 1 24.0 parts of 98% sulfuric acid and 80% of 1,2-dichloroethane.
While stirring 8 parts, the temperature was raised to 80 ° C., and 121.2 parts of 25% aminoethyl-2-hydroxyethylsulfone sulfate aqueous solution was distilled off 1,2-dichloroethane and water to give water as a reaction system. It was added dropwise over 2 hours while being removed to the outside.
After completion of the dropwise addition, the mixture was refluxed at 80 to 85 ° C. for 5 hours to remove 1,2-dichloroethane and water to remove water out of the reaction system to complete the reaction. After completion of the reaction, the reaction product kept at 70 ° C was poured into ice water to separate the layers. The separated aqueous layer was neutralized to pH 1-2 with soda ash. The production rate of aminoethyl-2-sulfatoethylsulfone was 98%.

Example 2 98% sulfuric acid 30.0 parts, n-heptane 80.8 parts and 25
% Aminopropyl-2-hydroxyethylsulfone sulfate aqueous solution 132.4 parts under reduced pressure of 400 mmHg while stirring, and n-heptane and water are distilled off at 75 to 78 ° C. to remove water from the reaction system. The reaction was terminated by refluxing for 5 hours. After completion of the reaction, the reaction product kept at 70 ° C was poured into ice water to separate the layers. PH 1 of the separated aqueous layer with soda ash
Neutralized to ~ 2. The production rate of aminopropyl-2-sulfatoethylsulfone was 98%.

Example 3 1,2-dichloroethane or n used in Example 1 or 2
-When octane, toluene, xylene, mesitylene, methyl isobutyl ketone, monochlorobenzene or orthodichlorobenzene is used instead of heptane, aminoethyl-2-sulfatoethylsulfone or aminopropyl-2-sulfur is produced with a production rate of 98%. Furtoethyl sulfone was obtained.

EXAMPLE 4 172.5 parts of a 20% aqueous solution of N-ethyl- [2- (2-hydroxyethylsulfonyl) ethyl] amine sulfate was added to 202.5 parts of diatomaceous earth, 80 parts of toluene and 16.5% of 98% sulfuric acid.
Part, and heated to 110 to 112 ° C. with stirring,
While toluene and water were distilled off to remove water out of the reaction system, the reaction was continued at the same temperature for 6 hours. After completion of the reaction, the reaction product kept at 70 ° C. was poured into ice water, filtered and separated, and the obtained aqueous layer was neutralized to pH 1-2 with soda ash. The production rate of N-ethyl- [2- (2-sulfatoethylsulfonyl) ethyl] amine was 97%.

Example 5 A biaxial double-arm kneader moving at 60 revolutions per minute,
Add 195 parts of acetylaminoethyl-2-hydroxyethyl sulfone and 300 parts of diatomaceous earth. Then 9 to this
Inject 105 parts of 8% sulfuric acid. Then 500 mmHg
Under reduced pressure, 250 parts of xylene was added dropwise to 120 to 12
The reaction was terminated by mixing for 8 hours while distilling off acetic acid and water at 5 ° C. After pouring the obtained reaction product into ice water,
The mixture was filtered and separated, and the obtained aqueous layer was neutralized to pH 3 to 6 with soda ash. The production rate of aminoethyl-2-sulfatoethylsulfone was 95%.

Examples 6 to 10 The free form was obtained in the same manner as in Example 2 except that an equimolar amount of the compound shown in the second column of the following table was used in place of aminopropyl-2-hydroxyethylsulfone sulfate. The compound shown in the third column of the table below was obtained in good yield.

[0020]

Reference Example 1 The neutralized aqueous solution obtained in Example 4 was freeze-dried to obtain solid N-ethyl- [2- (2-sulfatoethylsulfonyl) ethyl] amine in a yield of 96.5%. It was This is reacted with polyfluoro-1-octanesulfonyl fluoride in the presence of triethylamine, and after the reaction is completed, an alkali is added to the reaction product, and the following formula C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ SO ₄ is added. _A water and oil repellent finishing agent (melting point: 123 to 125 ° C.) represented by ₂ CH = CH ₂ was obtained.

[0022]

INDUSTRIAL APPLICABILITY According to the method of the present invention, an amino ester compound represented by the above general formula (I) which is useful as an intermediate for a water / oil repellent finishing agent, a silver halide photographic hardening agent, a surfactant and the like is obtained. It can be industrially advantageously produced.

Claims (2)

[Claims] 1. When expressed in a free form, the following general formula (II) H—N (R)₁) -W₁-SO_TwoCH_TwoCH_TwoOH (II) [wherein W₁Is a halogen atom, hydroxy group, sulfa
Group, carboxy group, cyano group or sulfo group
Optionally substituted, -O- or -NR_Three-(Here
And R_ThreeIs a hydrogen atom or C₁~ C_FourRepresents an alkyl group
You. ) A straight-chain or branched C which may contain_Two~ C
₆R represents an alkylene group;₁Is a hydrogen atom, substituted
May be C₁~ C_FourAlkyl group, may be substituted
Phenyl group or -W₁-SO_TwoCH_TwoCH_TwoOH group
Represents ] The amino alcohol compound or
The N-acetylated product is separated from sulfuric acid or fuming sulfuric acid and water
Water or water and acetic acid under normal pressure or reduced pressure in an organic solvent
And react with the organic solvent while distilling off
In the free form, the following general formula (I) H-N (R_Two) -W_Two-SO_TwoCH_TwoCH_TwoOY (I) [wherein W_TwoIs a halogen atom, hydroxy group, sulfa
Group, carboxy group, cyano group or sulfo group
Optionally substituted, -O- or -NR_Three− (R_Three
Represents the same meaning as described above. ), Which may contain a straight chain
Shaped or branched C _Two~ C₆R represents an alkylene group;_Two
Is a hydrogen atom, optionally substituted C₁~ C_FourAlkyl
Group, optionally substituted phenyl group or -W_Two-SO
_TwoCH_TwoCH_TwoRepresents a group of OY ', Y and Y'are the same
Or differently, a hydrogen atom or -SO _ThreeRepresents H, but Y
And Y ′ are not hydrogen atoms at the same time, and R_Two
Is a hydrogen atom, optionally substituted C₁~ C_FourAlkyl
When it is a group or an optionally substituted phenyl group,
Y is not a hydrogen atom. ] Amino
Process for producing ester compound. 2. An aminoalcohol compound represented by the general formula (II) or its N-acetylated product according to claim 1 in an organic solvent which separates sulfuric acid or fuming sulfuric acid from water under normal pressure or reduced pressure. And reacting water or water with acetic acid while distilling off with the organic solvent, and then treating the resulting reaction product with water or ice. A method for producing an amino ester compound represented by I).